Activator for biocide

ABSTRACT

A biocide composition comprises an effective amount of a biocide and an effective amount of a biocide activator selected from the group consisting of an alkyl phosphate, an alkenyl phosphate, a hydroxyalkyl phosphate, a polyoxyalkylene alkyl ether phosphate, a salt thereof, a polyoxyalkylene alkenyl ether phosphate, a salt thereof, a polyoxyalkylene hydroxyalkyl ether phosphate and a salt thereof.

This application is a continuation of U.S. Ser. No. 08/166 597 now abandoned, filed Dec. 13, 1993, which is a continuation of Ser. No. 07/418 903 now abandoned, filed Oct. 5, 1989, which is a continuation of Ser. No. 07/139 720 now abandoned, filed Dec. 30, 1987, which is a division of Ser. No. 07/042 545 now abandoned, filed Apr. 24, 1987, which is a continuation of Ser. No. 06/725 028 now abandoned, filed Apr. 19, 1985.

The present invention relates to an activator for biocides.

Biocides such as insecticides, germicides, herbicides and plant growth regulators have been used in the form of an emulsion, wettable powder, flowable product, grains or powder.

The physical properties of the biocides have been modified variously so as to exhibit the activity of the active ingredient sufficiently. However, it has been impossible to further increase the effects of biocide.

It is quite significant to further increase the effects of known biocides, since the development of new biocides is now very difficult.

After intensive investigations, the inventors have found that specified compounds are effective in further activating various biocides. The present invention has been completed on the basis of this finding.

The invention provides a biocide composition which comprises an effective amount of a biocide and an effective amount of a biocide activator selected from the group consisting of an alkyl phosphate, an alkenyl phosphate, a hydroxyalkyl phosphate, a polyoxyalkylene alkyl ether phosphate, a salt thereof, a polyoxyalkylene alkenyl ether phosphate, a salt thereof, a polyoxyalkylene hydroxyalkyl ether phosphate and a salt thereof. The invention may be provided in the form of an emulsion concentrate which comprises 10 to 70 weight percent of the biocide and 10 to 50 weight percent of the biocide activator, 3 to 20 weight percent of an emulsifier and 10 to 50 percent weight of an organic solvent, or a dilute composition which comprises 100 to 5,000 ppm of the biocide, 200 to 10,000 ppm, preferably 500 to 5,000 ppm, of the biocide activator and a carrier for dilution. The diluent composition is usually prepared just in advance to use thereof.

The alkyl phosphates, polyoxyalkylene alkyl ether phosphates and salts of them according to the present invention may be prepared by known processes. For example, they are obtained by reacting an alcohol (if necessary, after addition of an alkylene oxide thereto) with phosphorus pentoxide and, if necessary, neutralizing the reaction product.

The starting alcohol has 1 to 22 carbon atoms and contains a straight-chain or branched alkyl group, an alkenyl group having double bond(s) or hydroxyl group(s) in the chain or a hydroxyalkyl group. The alcohol contains preferably 4 to 18 carbon atoms, 0 to 4, preferably 0 to 2 double bonds and 0 to 4, preferably 0 to 2, hydroxyl groups. The alcohols include, for example, butanol, 2-ethyhexanol, lauryl alcohol, stearyl alcohol and oleyl alcohol.

The alkylene oxides to be added to the alcohol to form a polyoxyalkylene chain include ethylene oxide, propylene oxide and butylene oxide. They may be used either alone or in the form of block or random adducts of two or more of them. The mol number of addition is 1 to 100, preferably 1 to 50.

The addition reaction may be carried out by a known process by, for example, introducing an alkylene oxide into an alcohol in the presence of an acid or alkaline catalyst at 50° to 200° C. under 1 to 5 kg/cm². The alcohol or polyoxyalkylene alkyl ether may be phosphated by various processes. For example, 3 mol of the alcohol or polyoxyalkylene alkyl ether is reacted with 1 mol of phosphorus pentoxide at 80° to 100° C. for about 6 h to obtain a corresponding phosphate easily. The obtained alkyl phosphate or polyoxyalkylene alkyl ether phosphate is a mixture of a monoester and a diester in substantially equal amounts. Though excellent effects are exhibited when the activator for biocides of the present invention is any of the monoester and the diester, particularly excellent effects are obtained when it is a monoester, particularly a polyoxyalkylene alkyl ether/phosphoric monoester or a salt thereof.

When said phosphate is neutralized with a base, a corresponding polyoxyalkylene alkyl ether phosphate salt is obtained. This ester salt also has an excellent activating effect. The salts include alkali metal, alkaline earth metal, monoethanolamine, diethanolamine, triethanolamine and ammonium salts.

When the activator for biocides of the present invention is used in combination with a biocide, the effect of the biocides can be increased 2 or 3-folds irrespective of the variety of the biocide.

The activator of the present invention is used in an amount of 0.05 to 20, preferably 1 to 15 parts by weight per part by weight of the biocide.

The biocide may be in the form of any of an emulsion, flowable product, wettable powder and powder. Therefore, other additives such as an emulsifying agent, dispersant and carrier may be incorporated therein according to the form of the biocide.

The activator of the present invention may be used by incorporating the same into the biocide of the above-mentioned form according to the formulation or by applying the same to a subject in combination with the biocide at the time of the application of the biocide in a diluted form. The activating effect according to the invention can be obtained in both cases.

Though the mechanism of such a remarkable activation of the biocide by the activator of the present invention has not been fully elucidated yet, it may be presumed that the activator for biocide of the present invention has an extremely high power of solubilizing the biocide irrespective of the structure of the biocide and, therefore, the biocide is finely divided and the penetration thereof through the surfaces of plants or into insects and germs is accelerated.

The present invention provides also a biocidal process characterized by spraying an emulsion (or dispersion) of a biocide containing the above-described activator.

Examples of the biocides which are activated by the activator of the present invention will be given below, which by no means limit the biocides to be activated according to the present invention. The activator of the present invention can be used safely without damaging the farm products. The insecticides include pyrethroid insecticides such as Fenvalerate [α-cyano-3-phenoxybenzyl-2-(4-chlorophenyl)-3-methylvalerate] and Pyrethroid [cyano(4-fluoro-3-phenoxyphenylmethyl-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate]; organophosphorus insecticides such as DDVP (2,2-dichlorovinyldimethyl phosphate), Sumithion (dimethyl-4-nitro-m-tolylphosphorothionate), Malathon {S-[1,2-bis(ethoxycarbonyl)ethyl]dimethylphosphorothiol thionate}, Dimethoate [dimethyl-S-(N-methylcarbamoylmethyl)phosphorothiol thionate), Elsan {S-[α-(ethoxycarbonyl)benzyl]dimethylphosphorothiol thionate) and Baycid [O,O-dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophosphate]; carbamate insecticides such as Bassa (O-butylphenyl methylcarbamate), MTMC (m-tolyl methylcarbamate), Meobal (3,4-dimethylphenyl-N-methylcarbamate), NAC (1-naphthyl-N-methylcarbamate); as well as Methomyl {methyl-N[(methylcarbamoxyl)oxy]thioacetimide} and Cartap {1,3-bis(carbamoylthio)-2-(N,N-dimethlamino)propane hydrochloride].

Examples of acaricides include Smite {2-[2-(p-tert-butylphenoxy)isopropoxy]isopropyl-2-chloroethyl sulfide}, Acricid (2,4-dinitro-6-sec-butylphenyl dimethylacrylate), Chlormit (isopropyl 4,4-dichlorobenzylate), Acar (ethyl 4,4-dichlorobenzylate), Kelthane [1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol], Citrazon (ethyl O-benzoyl-3-chloro-2,6-dimethoxybenzohydroxymate), Plictran (tricyclohexyltin hydroxide) and Omite [2-(p-tert-butylphenoxy) cyclohexyl-2-propinylsulfite].

Examples of the germicides include organosulfur germicides such as Dithane (zinc ethylenebisdithiocarbamate), maneb (manganese ethylenebisdithiocarbamate), thiuram [bis(dimethylthiocarbamoyl) disulfide], Benlate [methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate], Difolatan (N-tetrachloroethylthio-4-cyclohexane-1,2-dicarboxyimide), Daconol (tetrachloroisophthalonitrile), Pansoil (5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole), Thiophanate-methyl [1,2-bis(3-methoxycarbonyl-2-thioureido)benzene], Rabcide (4,5,6,7-tetrachlorophthaloid), Kitazin P (O,O-diisopropyl-S-benzyl phosphorothioate), Hinosan (O-ethyl-S,S-diphenyldithiophosphate) and Propenazol (3-allyloxy-1,2-benzothiazole 1,1-dioxide).

Examples of the herbicides include Stam (3,4-dichloropropionanilide), Saturn [S-(4-chlorobenzyl) N,N-diethylthiolcarbamate), Lasso (2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide), Glyphosate [N-(phosphonomethyl)glycins isopropylamine salt], DCMU [3-(3,4-dichlorophenyl)-1,1-dimethylurea) and Gramoxone (1,1'-dimethyl-4,4'-dipyridium dichloride].

Examples of the plant growth regulating agents include MH (maleic acid hydrazide) and Ethrel (2-chloroethylphosphonic acid).

EXAMPLES AND EFFECTS

The following examples will further illustrate the activators for biocides of the present invention.

Example 1

A compound of the present invention was dissolved in a commercially available herbicide (Karmex wettable powder, Simazine wettable powder, Paraquat solution or Glyphosate solution) to obtain a 0.2% solution. 10 ml of the solution was sprayed to each pot of crabgrass (a weed of Gramineae) which had been grown uniformly. The herbicidal effects of them were compared with one another. The crabgrasses used were in a three- or four-foliate period having a height of about 10 cm. Each pot had 25 crabgrasses. The dilution rate of said Karmex wettable powder, Simazine wettable powder, Paraquat solution or Glyphosate solution was 1/300. The herbicidal rate was determined by weighing the above-the-ground parts of the crabgrasses 10 days after the spraying and the results were represented by percentage based on the weight of untreated grasses. The results are shown in Table 1.

                  TABLE 1                                                          ______________________________________                                                   Herbicidal rate (%)                                                            Karmex Simazine                                                                wettable                                                                              wettable Paraquat Glyphosate                                            powder powder   solution solution                                    ______________________________________                                         Activator of the                                                               present invention                                                              POE(3) 2-ethylhexyl                                                                        84.0     67.2     98.2   100                                       phosphate                                                                      POE(3) POP(5) 2-                                                                           80.8     68.5     99.1   100                                       ethylhexyl phosphate                                                           POE(3) POP(5) 2-                                                                           81.0     68.9     99.0   100                                       ethylhexyl phosphate/                                                          diethanolamine                                                                 POE(10) octyl                                                                              78.4     70.5     100    100                                       phosphate                                                                      Potassium POE(10)                                                                          79.8     72.4     100    100                                       octyl phosphate                                                                POE(30) lauryl                                                                             85.7     80.2     100    100                                       phosphate                                                                      POE(30) lauryl                                                                             86.0     81.5     100    100                                       phosphate mono-                                                                ethanolamine                                                                   POE(60) POB(10)                                                                            78.8     82.4     100    100                                       palmityl phosphate                                                             Sodium POE(60)                                                                             72.1     82.0     100    100                                       POB(10) palmityl                                                               phosphate                                                                      POE(25) POP(10)                                                                            89.1     89.5     100    100                                       oleyl phosphate                                                                Ammonium POE(25)                                                                           89.5     87.8     100    100                                       POP(10) oleyl                                                                  phosphate                                                                      POE(80) linoleyl                                                                           88.4     88.1     100    100                                       phosphate                                                                      Calcium POE(80)                                                                            89.4     89.9     100    100                                       linoleyl phosphate                                                             2-Ethylhexyl                                                                               69.0     60.0     95.0   97.2                                      phosphate                                                                      Lauryl phosphate                                                                           70.1     72.5     90.4   90.0                                      Oleyl phosphate                                                                            75.2     79.0     94.0   92.0                                      No activator used                                                                          21.0     18.4     64.2   68.4                                      Comparative                                                                    POE(3) 2-ethylhexyl                                                                        51.2     42.8     69.0   70.0                                      ether                                                                          POE(10) octyl ether                                                                        49.0     40.4     72.0   78.4                                      POE(30) lauryl ether                                                                       52.5     54.5     72.0   80.5                                      POE(25) POP(10)                                                                            57.5     52.8     79.5   75.5                                      oleyl ether                                                                    POE(60) POB(10)                                                                            45.4     42.1     72.8   75.6                                      palmityl ether                                                                 POE(80) linoleyl ether                                                                     60.5     55.2     79.2   80.0                                      ______________________________________                                          Note:                                                                          Symbols POE, POP and POB represent polyoxyethylene, polyoxypropylene and       polyoxybutylene, respectively. The numerals in the parentheses represent       the mol number of addition.                                              

Example 2

Third-instar larvae of plant hoppers were cultured and the insecticidal effects of insecticides thereon were examined by the leaf dipping method 3 repetition. Each group consisted of 10 larvae. The insecticidal effects were compared with those in an untreated group 24 h after the treatment. The results are shown in Table 2.

The insecticides used were a Sumithion emulsion and a Malathon emulsion each diluted to a concentration of 1/2000. The concentration of the activator of the present invention was controlled to 0.1% based on the diluted emulsion.

                  TABLE 2                                                          ______________________________________                                                          Insecticidal rate (%)                                                          50% Sumithion                                                                           50% Malathon                                                          emulsion emulsion                                             ______________________________________                                         Activator of the present invention                                             POE(3) 2-ethylhexyl phosphate                                                                     84.5       80.5                                             POE(3) POP(5) 2-ethylhexyl phosphate                                                              82.5       78.4                                             POE(3) POP(5) 2-ethylhexyl phosphate                                                              82.5       78.5                                             diethanolamine                                                                 POE(10) octyl phosphate                                                                           80.5       80.0                                             Potassium POE(10) octyl phosphate                                                                 81.2       78.9                                             POE(30) lauryl phosphate                                                                          86.4       82.4                                             POE(30) lauryl phosphate                                                                          86.9       86.7                                             monoethanolamine                                                               POE(60) POB(10) palmityl phosphate                                                                78.5       80.0                                             Sodium POE(60) POB(10) palmityl                                                                   82.4       81.5                                             phosphate                                                                      POE(25) POP(10) oleyl phosphate                                                                   90.1       94.6                                             Ammonium POE(25) POP(10) oleyl                                                                    86.5       90.0                                             phosphate                                                                      POE(80) linoleyl phosphate                                                                        89.5       92.1                                             Calcium POE(80) linoleyl phosphate                                                                90.5       92.6                                             2-Ethylhexyl phosphate                                                                            68.2       60.0                                             Lauryl phosphate   75.1       72.0                                             Linoleyl phosphate 85.1       80.0                                             No activator used  49.0       40.0                                             Comparative                                                                    POE(3) 2-ethylhexyl ether                                                                         52.5       41.5                                             POE(10) octyl ether                                                                               55.0       40.5                                             POE(30) lauryl ether                                                                              55.5       42.8                                             POE(25) POP(10) oleyl ether                                                                       49.0       39.5                                             POE(60) POB(10) palmityl ether                                                                    50.5       40.0                                             POE(80) linoleyl ether                                                                            56.0       45.2                                             ______________________________________                                    

Example 3

Male imagines of two-spotted red spider were applied to leaf disks of kidney beans in three replications. Each group consisted of 30 imagines. After the culture at 25° C. for 24 h. 0.2 ml per each group of a test sample was sprayed by the chromatospray method. The insecticidal rate was determined by comparison with the results of an untreated group 24 h after the treatment. The acaricides used were Amitraz emulsion and Osadan wettable powder diluted to a concentration of 1/2000. The concentration of the activator of the present invention was controlled to 0.1% based on the diluted product. The results are shown in Table 3.

                  TABLE 3                                                          ______________________________________                                                           Insecticidal rate (%)                                                          20% Amitraz                                                                             20% Osadan                                                            emulsion emulsion                                            ______________________________________                                         Activator of the present invention                                             POE(3) 2-ethylhexyl phosphate                                                                      92.5       100                                             POE(3) POP(5) 2-ethylhexyl phosphate                                                               96.0       100                                             POE(3) POP(5) 2-ethylhexyl phosphate                                                               96.0       100                                             diethanolamine                                                                 PIE(10) octyl phosphate                                                                            98.0       95.4                                            Potassium POE(10) octyl phosphate                                                                  98.5       99.0                                            POE(30) lauryl phosphate                                                                           97.5       100                                             POE(30) lauryl phosphate                                                                           90.0       100                                             monoethanolamine                                                               POE(60) POB(10) palmityl phosphate                                                                 95.0       100                                             Sodium POE(60) palmityl phosphate                                                                  92.5       100                                             POE(25) POP(10) oleyl phosphate                                                                    100        100                                             Ammonium POE(25) POP(10) oleyl                                                                     100        100                                             phosphate                                                                      POE(80) linoleyl phosphate                                                                         100        100                                             Calcium POE(80) linoleyl phosphate                                                                 100        100                                             No activator used   58.2       64.2                                            ______________________________________                                    

It is apparent from Examples 1 to 3 that the activators of the present invention have an excellent activating effect. In addition, each composition as prepared in Examples 1 to 3 was diluted with water. The obtained dilute one was effective to improve the biocide activity. Each component content in the dilute compositions is given, below.

    ______________________________________                                         In the compositions of Example 1                                                      activator    2000   ppm                                                        Karmex       1660                                                              Simazine     1660                                                              Paraquat     800                                                               Round-Up     660                                                        In the compositions of Example 2                                                      activator    1000   ppm                                                        Sumithion    250                                                               Malathon     250                                                        In the compositions of Example 3                                                      activator    1000   ppm                                                        Dani-Cut     100                                                               Osadan       225                                                        ______________________________________                                     

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
 1. An agricultural insecticidal composition which consists essentially of an effective amount of O,O-dimethyl O-4-nitro-m-tolylphosphorothionate and an effective amount of an anionic substance for increasing the insecticidal rate of said insecticide; said anionic substance being a monoester of phosphoric acid selected from the group consisting of an alkyl phosphate, an alkenyl phosphate, a hydroxyalkyl phosphate, a polyoxyalkylene alkyl ether phosphate, a polyoxyalkylene alkenyl ether phosphate, a polyoxyalkylene hydroxyalkyl ether phosphate, and salts thereof; the number of alkylene oxide units being from 1-100, the number of carbon atoms in the alkyl or alkenyl group being from 1-22 and said alkyl group being straight-chained or branched and the salt being selected from the group consisting of alkali metal salts, alkaline earth metal salts, monoethanol-amine salts, diethanolamine salts, triethanolamine salts and ammonium salts, the weight ratio of said substance/said insecticide being in the range of 1/1 to 15/1.
 2. A composition as claimed in claim 1, in which said substance is selected from the group consisting of an alkyl phosphate and an alkenyl phosphate.
 3. A composition as claimed in claim 1, in which said substance is selected from the group consisting of a hydroxyalkyl phosphate and a polyoxyalkylene hydroxyalkyl ether phosphate.
 4. A method of controlling insects, which comprises applying to a site containing insects an insecticidally effective amount of the composition as defined in claim
 1. 5. A composition as claimed in claim 1, in which said substance is anionic and is selected from the group consisting of a polyoxyalkylene alkylether phosphate, a polyoxyalkylene alkenyl ether phosphate, and salts thereof.
 6. A composition as claimed in claim 5, in which said substance is a polyoxyalkylene alkylether phosphate, or a salt thereof, the number of alkylene oxide units is from 1-50 and the number of carbon atoms in the alkyl group is from 4-18.
 7. A composition as claimed in claim 5, in which said substance is a polyoxyalkylene alkenylether phosphate, or a salt thereof, the number of alkylene oxide units is from 1-50 and the number of carbon atoms in the alkenyl group is from 4-18.
 8. A composition as claimed in claim 5, in which said substance is a polyoxyalkylene alkylether phosphate, or a salt thereof, the alkylene group is selected from the group consisting of ethylene and propylene and the alkyl group is selected from the group consisting of butyl, 2-ethylhexyl, lauryl and tridecyl.
 9. A composition as claimed in claim 5, in which said substance is a polyoxyalkylene alkenylether phosphate, or a salt thereof, the alkylene group is selected from the group consisting of ethylene and propylene and the number of alkylene oxide units is from 1-50 and said alkenyl group is oleyl.
 10. A composition as claimed in claim 5, in which said substance is a polyoxyalkylene alkylether phosphate.
 11. A composition as claimed in claim 8, in which the number of alkylene oxide units is from 1-50, said alkyl group is lauryl and said salt is monoethanolamine.
 12. An agricultural insecticidal composition which consists essentially of an effective amount of O,O-dimethyl O-4-nitro-m-tolylphosphorothionate and an effective amount of an anionic substance for increasing the insecticidal rate of said insecticide; said substance being a monoester of phosphoric acid selected from the group consisting of poxlyoxyethylene laurylether phosphate and polyoxyethylene laurylether phosphate monoethanol amine salt; the weight ratio of said substance/said insecticide being in the range of 1/1 to 15/1.
 13. A composition as claimed in claim 12, in which said substance is polyoxyethylene laurylether phosphate.
 14. A composition as claimed in claim 12, in which said substance is polyoxyethylene laurylether phosphate monoethanol amine salt.
 15. A method of controlling insects which comprises applying to a site containing insects an insecticidally effective amount of a composition as defined in claim
 12. 16. A method of controlling insects which comprises applying to a site containing insects an insecticidally effective amount of a composition as defined in claim
 13. 17. A method of controlling insects which comprises applying to a site containing insects an insecticidally effective amount of a composition as defined in claim
 14. 